Garnet-based phosphor ceramic sheets for light emitting device

ABSTRACT

Some embodiments disclosed herein include a lighting apparatus having a composite. The composite may include a first emissive layer and a second emissive layer. The first emissive layer may include a first garnet phosphor having a common dopant. The second emissive layer may include a second garnet phosphor having the common dopant. In some embodiments, the first emissive layer and the second emissive layer are fixed together. Some embodiments disclosed herein include efficient and economic methods of making the composite. The method may include, in some embodiments, sintering an assembly that includes pre-cursor materials for the first emissive layer and the second emissive layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of priority to U.S.Application No. 61/315,763, filed Mar. 19, 2010. The priority documentis hereby incorporated by reference in its entirety.

BACKGROUND

1. Field

The present application relates to a lighting apparatus including atranslucent composite of garnet-based emissive layers.

2. Description

Solid state light emitting devices such as light emitting diode (LED),organic light emitting diode (OLED) or sometimes called organicelectroluminescent device (OEL), and inorganic electroluminescent device(IEL) have been widely utilized for various applications such as flatpanel display, indicator for various instrument, signboard, andornamental illumination, etc. As the emission efficiency of these lightemitting devices continues to improve, applications that require muchhigher luminance intensity, such as automobile headlights and generallighting, may soon become feasible. For these applications, white-LED isone of the promising candidates and have attracted much attention.

Conventional white-LED have been manufactured based on the combinationof blue-LED and yellow light-emitting YAG phosphor powder dispersed inplastic encapsulant resin like epoxy and silicone. However, since theparticle size of YAG phosphor powder utilized for this system is around1-10 μm, the YAG powders dispersed in the encapsulant resin medium cancause strong light scattering. As a result, a considerable portion ofboth the incident light from the blue LED and the yellow emitting lightfrom YAG powders ends up being back scattered and dissipated as a lossof white light emission.

One approach to solve this problem is to use one or more phosphorceramic plates or laminated films that are positioned to receiveemissions from blue emitting light emitting diodes instead of phosphorpowders suspended in a transparent matrix. With optimized sinteringconditions, combined with the use of phosphors in nanoparticle form, itis possible to obtain a translucent or transparent ceramic. Since an LEDwith translucent/transparent phosphor ceramics has less backscatteringloss while maintaining, or in some cases, increasing the luminanceefficiency of the phosphor layer, it may emit stronger white light thanconventional YAG powder/resin system. In addition, since a ceramicplate/film is more stable against heat and light irradiation even underUV, temperature fluctuation of operational property, durability, andlifetime of the LED can be improved.

In order to achieve a lower correlated color temperature (CCT) andhigher color rendering index (CRI) in a YAG:Ce LED system, a redemitting component is needed. U.S. Patent Publication No. 2007/0215890,which is hereby incorporated by reference in its entirety, discloses theuse of a red phosphor platelet and a green phosphor platelet incombination with a blue LED to create a white light LED. U.S. Pat. No.7,446,343, which is hereby incorporated by reference in its entirety,uses yellow and red phosphor layers in LEDs, where the red phosphorcandidates need to have Eu³⁺ as dopant. Due to the use of differentdopants for the yellow and the red layers, they have to be preparedseparately. Furthermore, since Eu³⁺-doped compounds have a primaryabsorption region in the UV spectra instead of the blue visible light,some have resorted to using nitride or sulfide phosphors that can beactivated by blue light. For example, U.S. Pat. No. 7,361,938, which ishereby incorporated by reference in its entirety, discloses the use of ayellow emitting garnet (YAG:Ce) phosphor and a red emitting nitride orsulphide phosphor. However, these nitride or sulfide emissive elementsare not desirable due to the processing difficulties and/orchemical/thermal stability concerns. Thus there is a need for a whitelight LED device that utilizes blue light and green/yellow/red phosphorlayers and offers simplified processing.

Furthermore, some lighting systems, particularly those for daily andlandscape uses, as well as high power lighting systems for industrialuses, have a somewhat lower color temperature, T≦3500K, falling into thecategory of warm white lighting. If the color temperature is higher,T>4600K, the lighting system will be categorized as cold white light.For solid-state lighting purposes, warm white light is especiallypreferred because it has the same color temperature as standardincandescent bulbs. Thus, there is also a need for warm white light LEDdevices that utilize blue light and green/yellow/red phosphor layers, aswell as simple and economical processes for making these LED devices.

SUMMARY

Some embodiments disclosed herein provide a lighting apparatuscomprising a light source configured to emit radiation having awavelength of peak emission between about 360 nm and about 500 nm; and acomposite configured to receive at least a portion of the radiationemitted by the light source, wherein the composite comprises a firstemissive layer and a second emissive layer; wherein the first emissivelayer comprises a first garnet phosphor and the second emissive layercomprises a second garnet phosphor, and the first garnet phosphor andthe second garnet phosphor are doped with a common dopant.

In some embodiments, the second emissive layer is disposed between thefirst emissive layer and the light source. In some embodiments, thecomposite is substantially free of resin between the first emissivelayer and the second emissive layer.

In some embodiments, the first emissive layer and the second emissivelayer are sintered together. In some embodiments, the composite issubstantially free of an adhesive between the first emissive layer andthe second emissive layer. In some embodiments, each of the firstemissive layer and the second emissive layer has an at least 25%transmittance.

In some embodiments, the first garnet phosphor has a first wavelength ofpeak emission between about 495 nm and about 560 nm. In someembodiments, the second garnet phosphor has a second wavelength of peakemission between about 570 nm and about 650 nm.

In some embodiments, the first garnet phosphor is doped with the commondopant at a concentration in the range of about 0.05% to about 10.00% bymol.

In some embodiments, the second garnet phosphor is doped with the commondopant at a concentration in the range of about 0.05% to about 10.00% bymol.

In some embodiments, the common dopant is selected from the groupconsisting of Nd, Er, Eu, Cr, Yb, Sm, Tb, Ce and Pr.

In some embodiments, the first garnet phosphor is selected from thegroup consisting of Lu₃Al₅O₁₂:Ce, Ca₃Sc₂Si₃O₁₂:Ce, Y₃Al₅O₁₂:Ce,(Y,Tb)₃Al₅O₁₂:Ce and (Y, Gd)₃(Al, Ga)₅O₁₂:Ce. In some embodiments, thesecond garnet phosphor is Lu₂CaMg₂Si₃O₁₂:Ce. In some embodiments, thefirst garnet phosphor is Lu₃Al₅O₁₂:Ce, and the second garnet phosphor isY₃Al₅O₁₂:Ce.

In some embodiments, the first emissive layer and the second emissivelayer are ceramic plates or laminated ceramic tapes.

In some embodiments, the composite further comprises a third emissivelayer, wherein the third emissive layer comprises a third garnetphosphor having a third wavelength of peak emission. In someembodiments, the third wavelength of peak emission is between about 495nm and about 540 nm, the first wavelength of peak emission is betweenabout 540 and about 590 nm, and the second wavelength of peak emissionis between 570 nm and about 650 nm. In some embodiments, the firstemissive layer is disposed between the third emissive layer and thesecond emissive layer.

In some embodiments, the first garnet phosphor is selected from thegroup consisting of Lu₃Al₅O₁₂:Ce and Ca₃Sc₂Si₃O₁₂:Ce, and the thirdgarnet phosphor is selected from the group consisting of Y₃Al₅O₁₂:Ce,(Y,Tb)₃Al₅O₁₂:Ce. and (Y, Gd)₃(Al, Ga)₅O₁₂:Ce.

In some embodiments, the second garnet phosphor is Lu₂CaMg₂Si₃O₁₂:Ce.

In some embodiments, the first emissive layer, the second emissive layerand the third emissive layer are ceramic plates or laminated ceramictapes.

In some embodiments, the composite further comprises a firstnon-emissive layer disposed between the first emissive layer and thesecond emissive layer, wherein the first non-emissive layer issubstantially transparent. In some embodiments, the first non-emissivelayer is a ceramic. In some embodiments, the non-emissive layer consistsessentially of a garnet material. In some embodiments, the non-emissivelayer is substantially free of dopant. In some embodiments, the firstnon-emissive layer is substantially impermeable to diffusion of thecommon dopant.

In some embodiments, the composite further comprises a secondnon-emissive layer disposed between the first emissive layer and thethird emissive layer, wherein the second non-emissive layer issubstantially transparent.

In some embodiments, each of the first emissive layer, the secondemissive layer and the third emissive layer has an at least 25%transmittance.

In some embodiments, the wavelength of peak emission of the light sourceis between about 450 nm to about 500 nm.

Some embodiments provide a method of making a composite comprisingproviding an assembly comprising a first layer and a second layer,wherein the first layer comprises a first doped garnet phosphor, and thesecond layer comprises a second doped garnet phosphor, wherein the firstdoped garnet phosphor and the second doped garnet phosphor have a commondopant; and sintering the assembly to produce the composite.

In some embodiments, the method does not include applying an adhesive ora resin between the first layer and the second layer after sintering theassembly.

In some embodiments, providing the assembly comprises: providing a firstmixture comprising a first garnet phosphor in a solvent and a secondmixture comprising a second garnet phosphor in the solvent; forming atleast one first tape comprising the first garnet phosphor by casting thefirst mixture on a first substrate and allowing the solvent toevaporate; forming at least one second tape comprising the second garnetphosphor by casting the second mixture on a second substrate andallowing the solvent to evaporate; stacking the at least one first tapeand the at least one second tape together to form a tape stack; andcompressing and heating the tape stack to form the assembly.

In some embodiments, the method further comprises forming at least onenon-emissive tape, and disposing the at least one non-emissive tapebetween the at least one first tape and the at least one second tape.

In some embodiments, the at least one non-emissive tape consistsessentially of a garnet material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-C depict exemplary lighting apparatuses having a composite withtwo or more emissive layers.

FIG. 2 shows a preparation flow diagram for one embodiment of formingthe composite by molding and sintering.

FIG. 3 shows a preparation flow diagram for one embodiment of formingthe composite by laminating and sintering.

FIG. 4 shows the chromaticity of an exemplary YAG:Ce/Lu1:Ce laminatedcomposite excited by a blue emitting LED.

FIG. 5 shows the emission spectrum of an exemplary YAG:Ce/Lu1:Celaminated composite excited by a blue emitting LED.

DETAILED DESCRIPTION

Disclosed herein are lighting apparatuses having a composite comprisingtwo or more emissive layers, each emissive layer having a garnetphosphor doped with a common dopant. Applicants have discovered thatusing a common dopant within the composite provides superior absorptionefficiency. In particular, the absorption efficiency is improved at theexcitation wavelength ranging from 360 nm to about 500 nm (preferablyabout 460 nm). Additionally, by using garnet materials for each emissivelayer, the composite exhibits superior transparency, and reducedcracking or warping during heating or cooling.

Also disclosed are efficient and economic processes for making thegarnet phosphors. Conventional methods for making a composite withmultiple emissive layers require sintering each layer under separateconditions and subsequently stacking the emissive layers to form acomposite. Some embodiments disclosed herein provide for sintering thecomposite in a single step to reduce the cost and time necessary toprepare the composite. The composite can be sintered in a single step,in part, because the similar garnet materials allow sintering under thesame conditions. Furthermore, the common dopant among each layer reducesdopant diffusion problem during the sintering step, and eliminates theneed to sinter each layer separately. These and other advantages may beobtained through the teachings of the present application.

Lighting Apparatus

Some embodiments provide a lighting apparatus having a light source anda composite configured to receive at least a portion of the radiationemitted by the light source. The composite comprises a first emissivelayer and a second emissive layer. The first emissive layer comprises afirst garnet phosphor, and the second emissive layer comprises a secondgarnet phosphor, and the first garnet phosphor and the second garnetphosphor are doped with a common dopant.

The light source may, in some embodiments, be configured to emitradiation having a wavelength of peak emission between about 360 nm andabout 500 nm. In some embodiments, the light source emits radiationhaving a wavelength of peak emission between about 450 nm and about 500nm. Some embodiments include a light source that is a semiconductor LED.As an example, the light source may be an AlInGaN based single crystalsemiconductor material coupled to an electric source.

The first emissive layer comprises a first garnet phosphor doped with adopant that is the same as the dopant in the second emissive layer. Thusthe first and the second phosphors are doped with a common dopant. Thegarnet phosphor may have a composition D₃E₅O₁₂. In some embodiments, Dand E are independently selected from trivalent metals. In otherembodiments, D can be selected from Lu, Y, Gd, La, and Tb; and E can beselected from Al, Ga, and In. In preferred embodiments, D is selectedfrom Lu and Y, and E is Al. The common dopant may be selected from Nd,Er, Eu, Cr, Yb, Sm, Tb, Ce and Pr. In some embodiments, the commondopant is Ce.

The first garnet phosphor may include a concentration of common dopantthat is effective for the first garnet phosphor to exhibit fluorescencewhen exposed to radiation having a wavelength of peak emission in therange of about 360 nm to about 500 nm. In some embodiments, the commondopant has a concentration in the first garnet phosphor ranging fromabout 0.05 mol % to about 2 mol %. In some embodiments, the dopantconcentration in the first garnet phosphor may be from about 0.01 mol %to about 5 mol %, about 0.05 mol % to about 3 mol %, about 0.1 mol % toabout 1 mol %. Non-limiting examples of garnets include Y₃Al₅O₁₂:Ce, (Y,Tb)₃Al₅O₁₂:Ce, (Y, Gd)₃(Al, Ga)₅O₁₂:Ce, Lu₃Al₅O₁₂:Ce, andCa₃Sc₂Si₃O₁₂:Ce. In some embodiments, the first garnet phosphor isselected from Lu₃Al₅O₁₂:Ce and Ca₃Sc₂Si₃O₁₂:Ce. In some embodiments, thefirst garnet phosphor is Lu₃Al₅O₁₂:Ce, and the second garnet phosphor isY₃Al₅O₁₂:Ce.

The first garnet phosphor can be selected to adjust the emitted lightfrom the lighting apparatus. For example, the first garnet phosphor canbe selected to emit yellow or green light when exposed to the lightsource. A green emission can be obtained by selecting Lu₃Al₅O₁₂:Ceand/or Ca₃Sc₂Si₃O₁₂:Ce, while a yellow emission can be obtained byselecting Y₃Al₅O₁₂:Ce and/or (Y, Gd)₃(Al, Ga)₅O₁₂:Ce. In someembodiments, the first garnet phosphor has a first wavelength of peakemission between about 495 nm to about 590 nm. For example, the firstwavelength of peak emission may be between about 495 nm to about 540 nm,or alternatively the first wavelength of peak emission may be betweenabout 540 nm to about 590 nm

The second emissive layer may include a second garnet phosphor. Thesecond garnet phosphor may be a garnet doped with a common dopant (i.e.,the same dopant that is also present in the first garnet phosphor). Thegarnet may be, for example, any of those materials described above withrespect to the first garnet phosphor. Thus, for example, the garnet mayhave a composition D₃E₅O₁₂, where D and E are trivalent metals. Thesecond garnet phosphor may include a concentration of common dopant thatis effective for the second garnet phosphor to exhibit fluorescence whenexposed to radiation having a wavelength of peak emission in the rangeof about 360 nm to about 500 nm. The second garnet phosphor may alsoinclude a common dopant having a concentration ranging from about 0.05mol % to about 10.0 mol %. In some embodiments, the dopant concentrationin the second garnet phosphor may be from about 0.1 mol % to about 7.5mol %, about 0.25 mol % to about 5 mol %, about 0.5 mol % to about 3 mol% or about 0.75 mol % to about 2 mol %. In a preferred embodiment, thesecond phosphor is Lu₂CaMg₂Si₃O₁₂:Ce.

The second garnet phosphor may also be selected to adjust the emittedlight from the lighting apparatus. In some embodiments, the secondgarnet phosphor has a second wavelength of peak emission between about570 nm and about 650 nm. In some embodiments, the first wavelength ofpeak emission and the second wavelength of peak emission aresubstantially different (e.g., the wavelengths are at least about 10 nmapart).

The first garnet phosphor and the second garnet phosphor can bedifferent garnets. For example, the first garnet phosphor is Y₃Al₅O₁₂:Ceand the second garnet phosphor is Lu₂CaMg₂Si₃O₁₂:Ce. In someembodiments, the emission profile of the second garnet phosphor issubstantially different from the emission profile of the first garnetphosphor when both phosphors are exposed to radiation having awavelength of peak emission in the range of about 360 nm to about 500nm. In some embodiments, the first phosphor exhibits a wavelength ofpeak emission that is at least about 10 nm apart from any wavelength ofpeak emission exhibited by the second phosphor. In some embodiments, thesecond garnet phosphor is free of at least one garnet that is present inthe first garnet phosphor. As an example, the first garnet phosphorincludes Y₃Al₅O₁₂:Ce and the second garnet phosphor has no more thantrace amounts of Y₃Al₅O₁₂:Ce. In some embodiments, the concentration ofcommon dopant is substantially different for the first garnet phosphorand the second garnet phosphor. For example, the difference in dopantconcentration between the first garnet phosphor and the second garnetphosphor is at least 0.1 mol %, or preferably at least 0.5 mol %.

Some embodiments have a composite with a third emissive layer comprisinga third garnet phosphor. The garnet phosphor may be a garnet doped witha common dopant (i.e., a dopant also present in the first garnetphosphor and the second garnet phosphor). The garnet may be any of thosematerials described above with respect to the first garnet phosphorand/or the second garnet phosphor. In a preferred embodiment, the thirdgarnet phosphor is selected from Lu₃Al₅O₁₂:Ce, and Ca₃Sc₂Si₃O₁₂:Ce.

The third garnet phosphor may be selected to adjust the emitted lightfrom the lighting apparatus. In some embodiments, the third garnetphosphor has a third wavelength of peak emission between about 495 nmand about 540 nm. In some embodiments, the first wavelength of peakemission, the second wavelength of peak emission and the thirdwavelength of peak emission are substantially different (e.g., thewavelengths of peak emission are each at least about 10 nm apart).

Similar to above, the third garnet phosphor may be a different garnetfrom the first garnet phosphor and the second garnet phosphor. Forexample, the first garnet phosphor may be Y₃Al₅O₁₂:Ce, the second garnetphosphor may be Lu₂CaMg₂Si₃O₁₂:Ce and the third garnet phosphor may beLu₃Al₅O₁₂:Ce. In some embodiments, the third garnet phosphor is free ofat least one garnet which is present in the first garnet phosphor and atleast one garnet which is present in the second garnet phosphor. As anexample, the first garnet phosphor may include Y₃Al₅O₁₂:Ce, the secondgarnet phosphor may include Lu₂CaMg₂Si₃O₁₂:Ce, and the third garnetphosphor may have no more than trace amounts of Y₃Al₅O₁₂:Ce andLu₂CaMg₂Si₃O₁₂:Ce. In some embodiments, the concentration of commondopant is substantially different for each of the first garnet phosphor,the second garnet phosphor and the third garnet phosphor.

The composite may optionally include one or more non-emissive layers.The diffusion or migration of dopants between layers may reduceperformance of the lighting apparatus (e.g., by altering the emissionspectrum), and thus a non-emissive layer may be disposed betweenemissive layers to reduce diffusion of dopants between the emissivelayers. Thus, in some embodiments, the non-emissive layer issubstantially impermeable to diffusion of the common dopant. In someembodiments, the non-emissive layer is a ceramic. As an example, thenon-emissive layer may be a material selected from Y₃Al₅O₁₂, Lu₃Al₅O₁₂and Al₂O₃. In some embodiments, the non-emissive layer is a garnet. Forexample, the non-emissive layer may be Y₃Al₅O₁₂ or Lu₃Al₅O₁₂.

The non-emissive layer exhibits insignificant emission (if any) in thevisible spectrum when exposed to radiation ranging from about 360 nm toabout 500 nm relative to an emissive layer. In some embodiments, thenon-emissive layer consists essentially of a material selected from agarnet, Al₂O₃ and combinations thereof. That is, the non-emissive layermay include a garnet, Al₂O₃ and other materials that do notsubstantially alter the non-emissive property. For example, thenon-emissive layer may comprise a garnet material, but not the amount ofdopant effective to result in emission. In some embodiments, thenon-emissive layer consists essentially of a garnet. In someembodiments, the non-emissive layer is free of dopant (e.g., no morethan trace amounts of dopant).

In some embodiments, the total light transmittance of each of theemissive layers at the peak wavelength of emission, or the peakwavelength of the photoluminescent spectrum of the phosphor material, isat least about 25% of the theoretical total light transmittance,preferably at least about 40% of the theoretical total lighttransmittance, preferably at least about 60% of the theoretical totallight transmittance. In some embodiments, the total light transmittanceof each of the non-emissive layers is also at least about 60% of thetheoretical total light transmittance, preferably at least about 70% ofthe theoretical total light transmittance, more preferably at leastabout 80% of the theoretical total light transmittance.

The layers of the composite, such as the emissive and non-emissivelayers, may be coupled together. In some embodiments, the layers arecoupled together by sintering. In some embodiments, the layers arecoupled together by sintering the layers while adjacent layers are incontact. As an example, precursor materials (e.g., a mold or laminatedtapes) for each layer are stacked to form an assembly. The assembly canthen be sintered such that adjacent layers are fixed together. In someembodiments, the composite may be coupled together without using a resinand/or adhesive. In some embodiments, the composite is substantiallyfree of resin and adhesive between adjacent layers. A composite is“substantially free of resin” when free of an effective amount of resinto fix the two layers together. For example, a composite having a firstemissive layer and second emissive layer can be substantially free ofresin between the first emissive layer and the second emissive layer.Accordingly, the amount of resin (if any) between the first emissivelayer and the second emissive layer is insufficient to fix the layerstogether. In some embodiments, the composite is substantially free ofadhesive between adjacent layers.

FIG. 1A is an exemplary lighting apparatus having a composite with twoemissive layers. A submount 100 has a light source 105 (e.g., a LED)mounted thereon. First emissive layer 110 is disposed above the secondemissive layer 115 and receives at least a portion of the radiationemitted from the light source 105. Second emissive layer 115 is disposedbetween the conventional base LED 105 and the first emissive layer 110.The second emissive layer 115 receives at least a portion of theradiation emitted from the light source 105. An optional encapsulantresin 120 is placed over the light source 105, the first emissive layer110 and the second emissive layer 115. In some embodiments, the firstemissive layer 110 and the second emissive layer 115 are fixed togetherto form a composite.

FIG. 1B is another exemplary lighting apparatus having a composite withtwo emissive layers and one non-emissive layer. Non-emissive layer 125is interposed between the first emissive layer 110 and the secondemissive layer 115. In an embodiment, the first emissive layer 110, thesecond emissive layer 115, and the non-emissive layer 125 are fixedtogether to form a composite.

FIG. 1C is an exemplary lighting apparatus having a composite with threeemissive layers. First emissive layer 110 is interposed between thesecond emissive layer 115 and the third emissive layer 130. The thirdemissive layer 130 is configured to receive at least a portion of theradiation emitted from the light source 105. In some embodiments, thefirst emissive layer 110, the second emissive layer 115, and the thirdemissive layer 130 are fixed together to form a composite.

The location of the various components (e.g., the lights source 105,first emissive layer 110, etc.) in the lighting apparatus is notparticularly limited. In some embodiments, the components are configuredso that both the first emissive layer and the second emissive layerreceive at a least a portion of the radiation emitted from the lightsource. Light emitted from the second emissive layer may be reabsorbedby the first emissive layer, which can diminish the efficiency and/orCRI of the lighting apparatus. Thus, the first emissive layer and thesecond emissive layer may be configured to reduce emitted light from thesecond emissive layer that is received by the first emissive layer. Insome embodiments, the second emissive layer is disposed at leastpartially between the light source and the first emissive layer. In someembodiments, the emission layers are configured so that there is littleoverlap between the emission spectrum of the second emissive layer andthe excitation spectrum of the first emissive layer. By minimizing theoverlap, only a small amount of light emitted from the second layer canbe absorbed by the first emissive layer. As a result, the efficiencyand/or CRI of the lighting apparatus is not compromised or reduced.

The phosphor compositions may be encapsulated in a mold (e.g., asillustrated by encapsulated phosphor powder 120). For example, thecomposition may be formed into a mold by encapsulating the firstphosphor and the second phosphor in a resin, such as an epoxy orsilicone. Examples and methods for encapsulating the phosphors aredisclosed in U.S. Pat. Nos. 5,998,925 and 6,069,440, both of which arehereby incorporated by reference in their entirety.

By selecting appropriate emissive layers, the lighting apparatus canexhibit a CRI of at least 70 when exposed to light. In otherembodiments, the CRI is at least 72; at least 75; or at least 80. TheCRI refers to the ability to render various colors and has valuesranging from 0 to 100, with 100 being the best. The reference correlatedcolor temperature (CCT) for the CRI may be in the range about 2000 K toabout 4000K; in the range of about 2500 K to about 3500 K; or about2600K to about 3400 K.

Molding and Sintering to Form Composites

The lighting apparatus can include a first emissive layer having a firstgarnet phosphor and a second emissive layer having a second garnetphosphor (e.g., as illustrated in FIGS. 1A-C). The emissive layers may,in some embodiments, be ceramic plates. In some embodiment, thenon-emissive layer can be a ceramic plate. The ceramic plates may befixed together to form a composite.

In some embodiments, each ceramic plate independently includes amultiphasic material having about 85% to about 99.99% by volume of anemissive phase (e.g., the first garnet phosphor or the second garnetphosphor) and about 15% to about 0.01% by volume of a non-emissivephase. In some embodiments, the lighting apparatus may include a firstceramic plate having at least 85% by volume of the first phosphor, and asecond ceramic plate having at least 85% by volume of the secondphosphor. The ceramic plates are configured to receive at least aportion of light emitted from a light source.

The ceramic plates may be prepared by molding and sintering phosphormixtures. Exemplary ceramic plates and methods of making the same aredisclosed U.S. Publication No. 2009/0212697, which is herebyincorporated by reference in its entirety. FIG. 2 shows a preparationflow diagram for one embodiment of forming the composite by molding andsintering.

First, raw garnet phosphor powders are provided, such as the firstgarnet phosphor and the second garnet phosphor described herein. The rawpowders may be prepared using any conventional or suitable methods, suchas the flow-based thermochemical synthetic routes described herein. Insome embodiments, raw powders of phosphor materials used to make thecomposite are typically nano-sized particles with average particle sizeno greater than about 1000 nm, preferably no greater than about 500 nm,more preferably no greater than 200 nm. If the particle size is greaterthan about 1000 nm, it can be very difficult to make total lighttransmittance higher than about 50%, because such large particles do noteasily fuse with each other even at a high temperature and high pressuresintering condition. The result would be a tendency for a lot of airvoids to remain in the ceramic plate. On the other hand, nano-sizedparticles can easily fuse with each other, which enable us to preparefine and air void free ceramic plates.

The raw materials are not required to have the same composition orcrystal structure of resultant phosphor ceramic plate. For example, aYAG:Ce ceramic plate may be made by using YAG:Ce powders, Y—Al—O—Cecontaining amorphous powders, a mixture of YAlO₃:Ce and Al₂O₃ powders, amixture of Y₂O₃, Al₂O₃, and CeO₂ powders, and any combination thereof.

In some embodiments, small quantities of flux materials (e.g., sinteringaids) may be used in order to improve sintering properties if desired.In some embodiments, the sintering aids may include, but are not limitedto, tetraethyl orthosilicate (TEOS), colloidal silica, lithium oxide,titanium oxide, zirconium oxide, magnesium oxide, barium oxide, calciumoxide, strontium oxide, boron oxide, or calcium fluoride. Additionalsintering aids include, but are not limited to, alkali metal halidessuch as NaCl or KCl, and organic compounds such as urea. In someembodiments, the sintered ceramic plate comprises between about 0.01%and about 5%, between about 0.05% and about 5%, between about 0.1% andabout 4%, or between about 0.3% and about 1% by weight of the fluxmaterial(s) or sintering aid(s). The sintering aid can be intermixedwith the raw materials. For example, in some embodiments, tetraethylorthosilicate (TEOS) can be added to the raw materials to provide thedesired amount of sintering aid. In one embodiment, about 0.05% to about5% by weight of TEOS is provided to the sintered ceramic plate. In someembodiments, the amount of TEOS may be between about 0.3% and about 1%by weight.

Various plasticizers may also be included, in some embodiments, toreduce the glass transition temperature and/or improve flexibility ofthe ceramic. Non-limiting examples of plasticizers includedicarboxylic/tricarboxylic ester-based plasticizers, such asbis(2-ethylhexyl) phthalate, diisononyl phthalate,bis(n-butyl)phthalate, butyl benzyl phthalate, diisodecyl phthalate,di-n-octyl phthalate, diisooctyl phthalate, diethyl phthalate,diisobutyl phthalate, and di-n-hexyl phthalate; adipate-basedplasticizers, such as bis(2-ethylhexyl)adipate, dimethyl adipate,monomethyl adipate, and dioctyl adipate; sebacate-based plasticizers,such as dibutyl sebacate, and maleate; dibutyl maleate; diisobutylmaleate; polyalkylene glycols such as polyethylene glycol, polypropyleneglycol, and copolymers thereof; benzoates; epoxidized vegetable oils;sulfonamides, such as N-ethyl toluene sulfonamide,N-(2-hydroxypropyl)benzene sulfonamide, and N-(n-butyl)benzenesulfonamide; organophosphates, such as tricresyl phosphate, tributylphosphate; glycols/polyethers, such as triethylene glycol dihexanoate,tetraethylene glycol diheptanoate; alkyl citrates, such as triethylcitrate, acetyl triethyl citrate, tributyl citrate, acetyl tributylcitrate, trioctyl citrate, acetyl trioctyl citrate, trihexyl citrate,acetyl trihexyl citrate, butyryl trihexyl citrate, and trimethylcitrate; alkyl sulphonic acid phenyl ester; and mixtures thereof.

In some embodiments, the mixing and molding process may be made easierby occasionally adding binder resin and solvent to the raw powders. Abinder is any substance that improves adhesion of the particles of thecomposition being heated to form a composite. Some non-limiting examplesof binders include polyvinyl alcohol, polyvinyl acetate, polyvinylchloride, polyvinyl butyral, polystyrene, polyethylene glycol,polyvinylpyrrolidones, polyvinyl acetates, and polyvinyl butyrates, etc.In some, but not all, circumstances, it may be useful for the binder tobe sufficiently volatile that it can be completely removed or eliminatedfrom the precursor mixture during the sintering phase. Solvents whichmay be used in include, but not limited to water, a lower alkanol suchas but not limited to denatured ethanol, methanol, isopropyl alcohol andmixtures thereof, preferably denatured ethanol, xylenes, cyclohexanone,acetone, toluene and methyl ethyl ketone, and mixtures thereof. In apreferred embodiment, the solvent is a mixture of xylenes and ethanol.

The mixing process can be done using a mortar and pestle, ball millingmachine, bead milling machine or other equivalent equipments. For themolding process, a simple die for tablet molding, hot isostatic pressing(HIP), or cold isostatic pressing (CIP) may be utilized. In someembodiments, controlled quantities of raw powders are loaded in a moldfollowed by applying pressure to form the plate.

Two or more molds are then stacked to form an assembly, which issubsequently sintered to form a composite. The arrangement of the moldswill determine the configuration of the final composite. Thus, forexample, an assembly may include a first mold having the first garnetphosphor and a second mold having the second garnet phosphor. Thisassembly can then be sintered to form a composite including the firstemissive layer having the first phosphor and the second emissive layerhaving the second phosphor. As an example, a composite including thefirst emissive layer 110 and the second emissive 115, as illustrated inFIG. 1A. Accordingly, a person of ordinary skill, guided by theteachings of the present application, can prepare various compositeconfigurations, such as those disclosed above, by appropriately stackingthe molds prior to sintering.

As disclosed above, non-emissive layers may also be included in thecomposite. A non-emissive layer may be prepared, for example, bypreparing a mold of YAG powder that excludes amounts of dopant that areeffective to produce fluorescence. The mold may be included in thestacked assembly that is subsequently sintered to form the composite.

The assembly is then sintered at a high temperature that does not exceedthe melting point of the resultant phosphor materials. Thus, bysintering the assembly having two or more molds, a single sinteringprocess is used to prepare a composite having two or more emissivelayers. The emissive layers in the composite, in some embodiments, arecoupled together upon completion of the sintering process. In someembodiments, the composite is fixed together upon completion of thesintering process.

Any kinds of suitable ceramic sintering techniques can be used toprepare translucent ceramic plates. In some embodiments, sintering maybe carried out while applying pressure. Sintering conditions such as thetemperature profile, atmosphere, pressure, and duration depend on thetype of phosphor material.

Laminating and Sintering to Form Composites

The composite may be formed by laminating and sintering two or more casttapes, where the cast tapes can include the first phosphor and/or thesecond phosphor. Examples and methods of laminating and sintering two ormore cast tapes are disclosed in U.S. Pat. No. 7,514,721 and U.S.Publication No. 2009/0108507, both of which are hereby incorporated byreference in their entirety. FIG. 3 shows a preparation flow diagram forone embodiment of forming the ceramic plate by laminating and sintering.

First, the particle size of the raw materials (e.g., nitrate or oxidebased raw materials, such as Y₂O₃ and Al₂O₃ for forming YAG) mayoptionally be adjusted to reduce cracking in the cast tapes fromcapillary forces during evaporation of solvents. For example, theparticle size can be adjusted by pre-annealing raw material particles toobtain the desired particle size. Raw material particles can bepre-annealed in the temperature range of about 800° C. to about 1800° C.(or more preferably 1000° C. to about 1500° C.) to obtain the desiredparticle size. The pre-annealing may occur in a vacuum, air, O₂, H₂,H₂/N₂, or a noble gas (e.g., He, Ar, Kr, Xe, Rn, or combinationsthereof). In an embodiment, each of the raw materials (e.g., Y₂O₃ andAl₂O₃ for forming YAG) is adjusted to be about the same particle size.In another embodiment, the particles have a BET surface area in therange of about 0.5 m²/g to about 20 m²/g (preferably about 1.0 m²/g toabout 10 m²/g, or more preferably about 3.0 m²/g to about 6.0 m²/g).

A slurry may then be prepared for subsequently casting into a tape.Pre-made phosphors (e.g., phosphors prepared by flow-basedthermochemical synthetic routes described herein) and/or stoichiometricamounts of raw materials can be intermixed with various components toform a mixture. Exemplary components for the mixture include, but arenot limited to, dopants, dispersants, plasticizers, binders, sinteringaids and solvents. The dopants, sintering aids, plasticizers, bindersand solvents may be the same as those described above with respect tothe molding and sintering process.

In some embodiments, the dispersants can be Flowen, fish oil, long chainpolymers, steric acid, oxidized Menhaden fish oil, dicarboxylic acidssuch succinic acid, orbitan monooleate, ethanedioic acid, propanedioicacid, pentanedioic acid, hexanedioic acid, heptanedioic acid,octanedioic acid, nonanedioic acid, decanedioic acid, o-phthalic acid,p-phthalic acid and mixtures thereof.

The mixture may then be subjected to comminution to form a slurry by,for example, ball milling the mixture for a time period in the range ofabout 0.5 hrs. to about 100 hrs. (preferably about 6 hrs. to about 48hrs., or more preferably about 12 hrs. to about 24 hrs.). The ballmilling may utilize milling balls that include materials other than thecomponents intermixed within the mixture (e.g., the milling balls may beZnO₂ for a mixture that forms YAG). In an embodiment, the ball millingincludes isolating the milling balls after a period of time byfiltration or other known methods of isolation. In some embodiments, theslurry has a viscosity in the range of about 10 cP to about 5000 cP(preferably about 100 cP to about 3000 cP, or more preferably about 400cP to 1000 cP).

Third, the slurry may be cast on a releasing substrate (e.g., a siliconecoated polyethylene teraphthalate substrate) to form a tape. Forexample, the slurry may be cast onto a moving carrier using a doctorblade and dried to form a tape. The thickness of the cast tape can beadjusted by changing the gap between the doctor blade and the movingcarrier. In some embodiments, the gap between the doctor blade and themoving carrier is in the range of about 0.125 mm to about 1.25 mm(preferably about 0.25 mm to about 1.00 mm, or more preferably about0.375 mm to about 0.75 mm). Meanwhile, the speed of the moving carriercan have a rate in the range of about 10 cm/min. to about 150 cm/min.(preferably about 30 cm/min. to about 100 cm/min., or more preferablyabout 40 cm/min. to about 60 cm/min.). By adjusting the moving carrierspeed and the gap between the doctor blade and moving carrier, the tapecan have a thickness between about 20 μm and about 300 μm. The tapes mayoptionally be cut into desired shapes after casting.

Two or more tapes are laminated to form an assembly. The lamination stepcan include stacking two or more tapes (e.g., 2 to 100 tapes arestacked) and subjecting the stacked tapes to heat and uniaxial pressure(e.g., pressure perpendicular to the tape surface). For example, thestacked tapes may be heated above the glass transition temperature(T_(g)) of the binder contained in the tape and compressed uniaxiallyusing metal dies. In some embodiments, the uniaxial pressure is in therange of about 1 to about 500 MPa (preferably about 30 MPa to about 60MPa). In some embodiments, the heat and pressure is applied for a timeperiod in the range of about 1 min. to about 60 min. (preferably about15 min. to about 45 min., or more preferably about 30 min.). Thelamination step may optionally include forming various shapes (e.g.,holes or pillars) or patterns into the assembly by, for example, usingshaped dies.

Some embodiments of the assembly include at least one tape having thefirst garnet phosphor and at least one tape having the second garnetphosphor. The arrangement of the stacked tapes is not particularlylimited, however the tapes may be stacked so all of the tapes includingthe first phosphor are stacked together and all of the tapes includingthe second phosphor are stacked together. Similar to the discussionabove with regard to the stacking of molds to form the assembly, theconfiguration of the stacked tapes will correspond with theconfiguration of the composite.

The assembly may be heated to form the composite. The heating step mayinclude a debinding process and a sintering process. The debindingprocess includes decomposing at least a portion of organic componentswithin the assembly (e.g., volatilize binders and plasticizers withinthe assembly). As an example, the assembly may be heated in air to atemperature in the range of about 300° C. to about 1200° C. (preferablyabout 500° C. to about 1000° C., or more preferably about 800° C.) at arate of about 0.1° C./min. to about 10° C./min. (preferably about 0.3°C./min. to about 5° C./min., or more preferably about 0.5° C./min. toabout 1.5° C./min). The exemplary heating step may also includemaintaining the temperature for a time period in the range of about 30min. to about 300 min, which may be selected based upon the thickness ofthe assembly.

The heating step also includes a sintering process to form thecomposite. The assembly may be sintered in a vacuum, air, O₂, H_(z),H_(z)/N₂, or a noble gas (e.g., He, Ar, Kr, Xe, Rn, or combinationsthereof) at a temperature in the range of about 1200° C. to about 1900°C. (preferably about 1300° C. to about 1800° C., or more preferablyabout 1350° C. to about 1700° C.) for a time period in the range ofabout 1 hr. to about 100 hrs (preferably about 2 hrs. to about 10 hrs.).In some embodiments, the debinding and sintering processes are completedin a single step.

The assembly may be sandwiched between cover plates during the heatingstep to reduce distortion (e.g., warping, cambering, bending, etc.) ofthe assembly. The cover plates may include materials having a meltingpoint above the temperatures applied during the heating step. Moreover,the cover plate may be sufficiently porous to permit transport ofvolatilized components through the covering plates. As an example, thecovering plate may be zirconium dioxide having a porosity of about 40%.

An optional reoxidation step may also be included to improve thetransmittance of the composite. Reoxidation can include exposing thecomposite to oxygen or air at a temperature in the range of about 1000°C. to about 1500° C. (preferably about 1400° C.) for a time period ofabout 30 min. to about 300 min. (preferably about 2 hrs.) at a heatingrate of about 1° C./min. to about 20° C./min. (preferably about 5°C./min.).

The lighting apparatus may include non-emissive layers (e.g.,non-emissive layer 125 illustrated in FIG. 1B). The non-emissive layercan be a ceramic plate which may also be prepared using similarlaminating and sintering procedures as those described above. Anon-emissive layer may be prepared, for example, by laminating andsintering a YAG powder into the assembly that excludes amounts of dopantthat are effective to produce fluorescence.

EXAMPLES

Additional embodiments are disclosed in further detail in the followingexamples, which are not in any way intended to limit the scope of theclaims.

Example 1 Warm White Light Emitting Composite

The following example demonstrates forming a composite for the emissionof warm white light.

Example 1.1 YAG:Ce

0.14923 mol (14.29 g) of Yttrium (III) nitrate hexahydrate (99.9% pure,Sigma-Aldrich), 0.25 mol (23.45 g) of Aluminum nitrate nonahydrate(99.97% pure, Sigma-Aldrich), and 0.015 mol (0.081 g) of Cerium (III)nitrate hexahydrate (99.99% pure, Sigma-Aldrich) were dissolved in 250ml of deionized water, followed by ultrasonication for 30 min to preparethe transparent precursor solution. This pre-cursor solution of 0.4 Mwas carried into a plasma reaction chamber via an atomization probeusing a liquid pump.

All deposition experiments were conducted with an RF induction plasmatorch (TEKNA Plasma System, Inc PL-35) operating at 3.3 MHz. For thedeposition experiments, the chamber pressure was kept at around 25kPa-35 kPa, and the RF generator plate power was in the range of 10-12kW. Both the plate power and the deposition pressure are user-controlledparameters. Argon was introduced into the plasma torch as both theswirling sheath gas and the central plasma gas via the gas inlet ports.Sheath gas flow was maintained at 30 slm (standard liters per minute),while central gas flow was 10 slm.

Reactant injection was performed using a radial atomization probe (TEKNAPlasma System, Inc SDR-772). The probe was positioned at the center ofthe plasma plume during reactant injection. The reactants were fed intothe plasma plume at a rate of 10 ml/min during deposition. Atomizationof the liquid reactant was performed with Argon as atomizing gasdelivered at a flow rate of 15 slm. The cooling water supply to theatomization probe was maintained at a flow rate of 4 slm and at apressure of 1.2 MPa, as recommended by the manufacturer.

Crystalline phases of the deposited particles were investigated usingX-ray diffraction (XRD) spectra obtained with a Bruker AXSmicro-diffractometer (CuKα). The crystalline phase of the obtainedsample was identified as a mixture of amorphous and yttrium aluminumperovskite (YAP). The average particle diameter (D_(avg)) was obtainedfrom BET surface area based on data acquired from a Micrometritics modelGemini 2365 gas sorptometer. The obtained D_(avg) of the sample was 75nm.

Example 1.2 Lu₂CaMg₂Si₃O₁₂:Ce

The procedure of Example 1.1 was followed except that 52.612 g ofLutetium nitrate hydrate (46.8% pure, Metall Rare Earth Limited,ShenZhen, P.R.China), 14.899 g of Calcium nitrate tetrahydrate (99%pure, Sigma-Aldrich), 32.374 g of Magnesium nitrate hexahydrate (99%pure, Fluka), 102.908 g of Aminopropylsilanetriol (25% in water,Gelest), and 0.543 g of Cerium (III) nitrate hexahydrate (99.99% pure,Sigma-Aldrich) were dissolved in 250 ml of deionized water, followed byultrasonication for 30 min to prepare the transparent precursorsolution. This precursor solution of 0.4 M was carried into a plasmareaction chamber via an atomization probe using a liquid pump.

Example 1.3 Preparation of Non-Emissive (Undoped) Material

The preparation of the non-emissive material was prepared similarly tothat described above, except that no Cerium (III) nitrate hexahydratewas added to 0.14923 mol (14.29 g) of Yttrium (III) nitrate hexahydrate(99.9% pure, Sigma-Aldrich), 0.25 mol (23.45 g) of Aluminum nitratenonahydrate (99.97% pure, Sigma-Aldrich).

Example 1.4 Preparation of Sintered Ceramic Plates of YAG:Ce PhosphorMaterial

Sintered ceramic plates were made using YAG:Ce phosphor nano-powders. 4g of nano-powder prepared by the method described above, 0.21 g ofpoly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (average Mw90,000-120,000 powder, Sigma-Aldrich), 0.012 g of fumed silica powder(CAB-O-SIL® HS-5, Cabot Corporation), and 10 ml of ethanol were wellmixed by mortar and pestle until the mixture slurry solution became verysmooth. By blowing hot air from a dryer and keeping the pestle moving,ethanol was completely removed, and dry powders were obtained. Then 120mg of the dry powders were spread out into a 3 mm diameter die(Product#: 0012-6646, 3 mm KBr Die Set, International CrystalLaboratories, Inc), followed by applying a pressure of 4000 psi usinghydraulic press. Then the obtained plates were sintered at 800° C. for 2hrs (heating rate of 2° C./min) using a box electrical furnace under anair ambient, and then at 1500° C. for 5 hrs (heating rate is 5° C./min)using tube electrical furnace under vacuum. The crystalline phase of allceramic plate samples was determined as yttrium aluminum garnet by XRD.

Example 1.5 Preparation of Sintered Ceramic Plates of Lu₂CaMg₂Si₃O₁₂:CePhosphor Material

The procedure of Example 1.4 was followed except that 4 g ofLu₂CaMg₂Si₃O₁₂:Ce, as prepared in Example 1.2, and the obtained plateswere sintered at 1400° C. for 5 hrs under vacuum.

Example 2 Laminated Composite of Emissive Layers

The following example demonstrates the emission of warm white light by acomposite formed by lamination.

Example 2.1 Non-Emissive Layers for Laminated Composite

A 50 ml high purity Al₂O₃ ball mill jar was filled with 55 g ofY₂O₃-stabilized ZrO₂ ball of 3 mm diameter. Then, in a 20 ml glass vial,0.153 g dispersant (Flowlen G-700. Kyoeisha), 2 ml xylene (FisherScientific, Laboratory grade) and 2 ml ethanol (Fisher Scientific,reagent alcohol) were mixed until the dispersant was dissolvedcompletely. The dispersant solution and tetraethoxysilane as sinteringaid (0.038 g, Fluka) were added to a ball mill jar.

Y₂O₃ powder (3.984 g, 99.99%, lot N-YT4CP, Nippon Yttrium Company Ltd.)with a BET surface area of 4.6 m²/g and Al₂O₃ powder (2.998 g, 99.99%,grade AKP-30, Sumitomo Chemicals Company Ltd.) with a BET surface areaof 6.6 m²/g were added to ball mill jar. The total powder weight was 7.0g and the ratio of Y₂O₃ to Al₂O₃ was at a stoichiometric ratio of 3:5. Afirst slurry was produced by mixing the Y₂O₃ powder, the Al₂O₃ powder,dispersant, tetraethoxysilane, xylenes, and ethanol by ball milling for24 hours.

A solution of binder and plasticizers was prepared by dissolving 3.5 gpoly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (Aldrich), 1.8 gbenzyl n-butyl phthalate (98%, Alfa Aesar), and 1.8 g polyethyleneglycol (Mn=400, Aldrich) in 12 ml xylene (Fisher Scientific, Laboratorygrade) and 12 ml ethanol (Fisher Scientific, reagent alcohol). A secondslurry was produced by adding 4 g of the binder solution into the firstslurry and then milling for another 24 hours. When ball milling wascomplete, the second slurry was passed through a syringe-aided metalscreen filter with pore size of 0.05 mm. Viscosity of second slurry wasadjusted to 400 centipoise (cP) by evaporating solvents in the slurrywhile stirring at room temperature. The slurry was then cast on areleasing substrate, e.g., silicone coated Mylar® carrier substrate(Tape Casting Warehouse) with an adjustable film applicator (Paul N.Gardner Company, Inc.) at a cast rate of 30 cm/min. The blade gap on thefilm applicator was set at 0.508 mm (20 mil). The cast tape was driedovernight at ambient atmosphere to produce a green sheet of about 140 μmthickness.

Example 2.2 YAG:Ce Layers

Plasma-produced yttrium aluminum oxide (with stoichiometryY:Al:O=3:5:12) powders (5.2 g) containing 0.2 mol % cerium with respectto yttrium with a BET surface area of about 20 m²/g was added to a highpurity alumina combustion boat followed by annealing in a tube furnace(MTI GSL-1600) at heating ramp of 3-5° C./min to 1250° C. in air or 3%H₂/97% N₂ for 2 hrs. Then, it was cooled down to room temperature at aramp of 5° C./min. Yellow color powder with a BET surface area of 4.6m²/g was obtained after annealing.

A 50 ml high purity Al₂O₃ ball mill jar was filled with 24 g Y₂O₃stabilized ZrO₂ ball of 3 mm diameter. Then, in a 20 ml glass vial,0.084 g dispersant (Flowlen G-700. Kyoeisha), 2 ml xylene (FisherScientific, Laboratory grade), and 2 ml ethanol (Fisher Scientific,reagent alcohol) were mixed until the dispersant was dissolvedcompletely. The dispersant solution and tetraethoxysilane as a sinteringaid (0.045 g 99.0% pure, Fluka) were added to a ball mill jar. Theannealed plasma YAG powder (3.0 g) with a BET surface area of 4.6 m²/g,was added to a ball mill jar. The first slurry was produced by mixingthe YAG powder, dispersant, tetraethoxysilane, xylenes, and ethanol byball milling for 24 hours.

A solution of binder and plasticizers was prepared by dissolving 5.25 gpoly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (Aldrich), 2.6 gbenzyl n-butyl phthalate (98%, Alfa Aesar), and 2.6 g polyethyleneglycol (Mn=400, Aldrich) in 18 ml xylene (Fisher Scientific, Laboratorygrade) and 18 ml ethanol (Fisher Scientific, reagent alcohol). A secondslurry was produced by adding 1.2 g of the binder solution into thefirst slurry and then milling another 24 hours. When ball milling wascomplete, the second slurry was passed through a syringe-aided metalscreen filter with pore size of 0.05 mm. The viscosity of the secondslurry was adjusted to 400 centipoise (cP) by evaporating solvents inthe slurry while being stirred at room temperature. The slurry was thencast on a releasing substrate, e.g., silicone coated Mylar® carriersubstrate (Tape Casting Warehouse) with an adjustable film applicator(Paul N. Gardner Company, Inc.) at a cast rate of 30 cm/min. The bladegap on the film applicator was set at 0.508 mm (20 mil). The cast tapewas dried overnight at ambient atmosphere to produce a yellow-coloredgreen sheet of about 140 μm thickness.

Example 2.3 Lu₂CaMg₂Si₃O₁₂:Ce

The procedure of Example 2.2 was followed except that 3.0 g ofLu₂CaMg₂Si₃O₁₂:Ce, which contained 1 mol % cerium with respect tolutetium, as prepared in Example 1.2, were used instead of YAG:Cepowder.

Example 2.4 Laminating Layers

The dried cast tape of the first phosphor material (300 μm thickness)comprising the annealed plasma YAG:Ce powders, the dried cast tape ofthe non-emissive material (100 μm thickness) comprising YAG with no Cepowder, as well as the dried cast tape comprising the annealed plasmaLu₂CaMg₂Si₃O₁₂:Ce powders (250 μm thickness) were cut into circularshapes of 13 mm diameter with a metal puncher. The respective pieces ofpunched circular-shaped tapes were placed between circular dies withmirror-polished surfaces and heated on a hot plate to 80° C., andsubsequently compressed in a hydraulic press at a uniaxial pressure of 5metric tons for 5 minutes. Laminated composites of emissive (firstphosphor material and second phosphor material) and non-emissive layerswere thus produced.

For debinding, laminated green sheets were sandwiched between ZrO₂ coverplates (1 mm in thickness, grade 42510-X, ESL Electroscience Inc.) andplaced on an Al₂O₃ plate of 5 mm thickness. The sandwiched laminate wasthen heated in a tube furnace in air at a ramp rate of 0.5° C./min to800° C. and held for 2 hours to remove the organic components from thegreen sheets to generate a preform.

After debinding, the preforms were annealed at 1500° C. in a vacuum of10⁻¹ Torr for 5 hours at a heating rate of 1° C./min to completeconversion from non-garnet phases of Y—Al—O in the non-emissive layer,including, but not limited to, amorphous yttrium oxides, YAP, YAM orY₂O₃ and Al₂O₃ to yttrium aluminum garnet (YAG) phase, and theconversion from amorphous Lu₂CaMg₂Si₃O₁₂:Ce to crystallizedLu₂CaMg₂Si₃O₁₂:Ce phase as well as increase the final YAG andLu₂CaMg₂Si₃O₁₂:Ce grain size.

Following the first annealing, the preforms were further sintered in avacuum of 10⁻³ Torr at about 1650° C. for 2 hours at a heating rate of5° C./min and a cooling rate of 10° C./min to room temperature toproduce a translucent YAG/YAG:Ce/Lu₂CaMg₂Si₃O₁₂:Ce/YAG ceramic sheet ofabout 0.60 mm thickness. When the laminated green sheets were annealedin the furnace with a graphite heater and carbon felt lining, thepreforms were embedded in sacrificial undoped YAG powders of 1 to 5 μmparticle size to prevent the samples from being partially reduced toconstituent metals due to strong reducing atmosphere. Brownish sinteredceramic sheets were reoxidized in a furnace under vacuum at 1400° C. for2 hrs at heating and cooling rates of 10° C./min and 20° C./minrespectively.

Example 2.5 Optical Measurements

Chromaticity measurements were performed with Otsuka Electronics MCPD7000 multi channel photo detector system together with required opticalcomponents such as optical fibers (Otuka Electronics), 12-inch diameterintegrating spheres (Gamma Scientific, GS0IS12-TLS, calibration lightsource (Gamma Scientific, GS-IS12-OP1) configured for total fluxmeasurement, and excitation light source (Cree blue-LED chip, dominantwavelength 455 nm, C455EZ1000-52001).

A blue LED with a peak wavelength of 455 nm was then placed at thecentral position of the integrating sphere and was operated with a drivecurrent of 25 mA. First the radiation power from the bare blue LED chipas excitation light was acquired. The light emitting face distance ofLED chip was 1 mm. A diced 2 mm×2 mm laminated sample was coated withparaffin oil having similar refractive index as common encapsulationresin such as epoxy (for example about 1.75) was then mounted a distanceof about 100 μm from LED chip. The radiation power of the combination ofthe composite laminate and the blue LED was then acquired.

As shown in FIG. 4, the composite YAG:Ce and Lu1 laminate, which wasprepared according to Examples 2.1-2.5, had CIE coordinates with Cy ofabout 0.3986±0.0025 and Cx of about 0.4328±0.0025, indicating a whitelight having a CT of about 3025K (“warm white”). The resultant compositeexhibited a CRI of about 70. Meanwhile, FIG. 5 shows the emissionspectrum the same YAG:Ce and Lu1 laminate by a blue LED with a peakwavelength of 455 nm.

1. A lighting apparatus comprising: a light source configured to emitradiation having a wavelength of peak emission between about 360 nm andabout 500 nm; and a composite configured to receive at least a portionof the radiation emitted by the light source, wherein the compositecomprises a first emissive layer and a second emissive layer; whereinthe first emissive layer comprises a first garnet phosphor and thesecond emissive layer comprises a second garnet phosphor, and the firstgarnet phosphor and the second garnet phosphor are doped with a commondopant.
 2. The lighting apparatus of claim 1, wherein the secondemissive layer is disposed between the first emissive layer and thelight source.
 3. The lighting apparatus of claim 1, wherein thecomposite is substantially free of resin between the first emissivelayer and the second emissive layer.
 4. The lighting apparatus of claim1, wherein the composite is substantially free of an adhesive betweenthe first emissive layer and the second emissive layer.
 5. The lightingapparatus of claim 1, wherein each of the first emissive layer and thesecond emissive layer has an at least 25% transmittance.
 6. The lightingapparatus of claim 1, wherein the first garnet phosphor has a firstwavelength of peak emission between about 495 nm and about 560 nm. 7.The lighting apparatus of claim 1, wherein the second garnet phosphorhas a second wavelength of peak emission between about 570 nm and about650 nm.
 8. The lighting apparatus of claim 1, wherein the first garnetphosphor is doped with the common dopant at a concentration in the rangeof about 0.05% to about 10.00% by mol.
 9. The lighting apparatus ofclaim 1, wherein the second garnet phosphor is doped with the commondopant at a concentration in the range of about 0.05% to about 10.00% bymol.
 10. The lighting apparatus of claim 1, wherein the common dopant isselected from the group consisting of Nd, Er, Eu, Cr, Yb, Sm, Tb, Ce andPr.
 11. The lighting emitting apparatus of claim 1, wherein the firstgarnet phosphor is selected from the group consisting of Lu₃Al₅O₁₂:Ce,Ca₃Sc₂Si₃O₁₂:Ce, Y₃Al₅O₁₂:Ce, (Y,Tb)₃Al₅O₁₂:Ce and (Y, Gd)₃(Al,Ga)₅O₁₂:Ce.
 12. The lighting emitting apparatus of claim 11, wherein thesecond garnet phosphor is Lu₂CaMg₂Si₃O₁₂:Ce.
 13. The lighting emittingapparatus of claim 11, wherein the first garnet phosphor isLu₃Al₅O₁₂:Ce, and the second garnet phosphor is Y₃Al₅O₁₂:Ce.
 14. Thelighting apparatus of claim 1, wherein the first emissive layer and thesecond emissive layer are ceramic plates or laminated ceramic tapes. 15.The lighting apparatus of claim 1, wherein the composite furthercomprises a third emissive layer, wherein the third emissive layercomprises a third garnet phosphor having a third wavelength of peakemission.
 16. The lighting apparatus of claim 15, wherein the thirdwavelength of peak emission is between about 495 nm and about 540 nm,the first wavelength of peak emission is between about 540 and about 590nm, and the second wavelength of peak emission is between 570 nm andabout 650 nm.
 17. The lighting apparatus of claim 15, wherein the firstemissive layer is disposed between the third emissive layer and thesecond emissive layer.
 18. The lighting apparatus of claim 15, whereinthe first garnet phosphor is selected from the group consisting ofLu₃Al₅O₁₂:Ce and Ca₃Sc₂Si₃O₁₂:Ce, and the third garnet phosphor isselected from the group consisting of Y₃Al₅O₁₂:Ce, (Y,Tb)₃Al₅O₁₂:Ce. and(Y, Gd)₃(Al, Ga)₅O₁₂:Ce.
 19. The lighting emitting apparatus of claim15, wherein the second garnet phosphor is Lu₂CaMg₂Si₃O₁₂:Ce.
 20. Thelighting apparatus of claim 1, wherein the composite further comprises afirst non-emissive layer disposed between the first emissive layer andthe second emissive layer, wherein the first non-emissive layer issubstantially transparent.
 21. A method of making a compositecomprising: providing an assembly comprising a first layer and a secondlayer, wherein the first layer comprises a first doped garnet phosphor,and the second layer comprises a second doped garnet phosphor, whereinthe first doped garnet phosphor and the second doped garnet phosphorhave a common dopant; and sintering the assembly to produce thecomposite.